PL200493B1 - 4−hydroxybiphenyl hydrazide derivatives - Google Patents
4−hydroxybiphenyl hydrazide derivativesInfo
- Publication number
- PL200493B1 PL200493B1 PL354483A PL35448300A PL200493B1 PL 200493 B1 PL200493 B1 PL 200493B1 PL 354483 A PL354483 A PL 354483A PL 35448300 A PL35448300 A PL 35448300A PL 200493 B1 PL200493 B1 PL 200493B1
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- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002585 base Substances 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 17
- 229940125890 compound Ia Drugs 0.000 claims description 11
- 239000012022 methylating agents Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002841 Lewis acid Substances 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000001035 methylating effect Effects 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 3
- 238000002360 preparation method Methods 0.000 abstract description 15
- 239000005653 Bifenazate Substances 0.000 abstract description 6
- VHLKTXFWDRXILV-UHFFFAOYSA-N bifenazate Chemical compound C1=C(NNC(=O)OC(C)C)C(OC)=CC=C1C1=CC=CC=C1 VHLKTXFWDRXILV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000642 acaricide Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- FGOJCPKOOGIRPA-UHFFFAOYSA-N 1-o-tert-butyl 4-o-ethyl 5-oxoazepane-1,4-dicarboxylate Chemical compound CCOC(=O)C1CCN(C(=O)OC(C)(C)C)CCC1=O FGOJCPKOOGIRPA-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- -1 isopropyl-2- (4-methoxy- [1,1'-biphenyl] -3-yl) hydrazine (biphenazate) carboxylate Chemical compound 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 150000004031 phenylhydrazines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PXTZQUZELQEHDH-UHFFFAOYSA-N 5-hydroxy-2-phenylbenzohydrazide Chemical class OC=1C=C(C(=CC1)C1=CC=CC=C1)C(=O)NN PXTZQUZELQEHDH-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010357 aspartame Nutrition 0.000 description 1
- 125000005604 azodicarboxylate group Chemical group 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PZQSQRCNMZGWFT-QXMHVHEDSA-N propan-2-yl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(C)C PZQSQRCNMZGWFT-QXMHVHEDSA-N 0.000 description 1
- STIVJHUWVYOBNK-UHFFFAOYSA-N propan-2-yl n-(2-hydroxy-5-phenylanilino)carbamate Chemical compound C1=C(O)C(NNC(=O)OC(C)C)=CC(C=2C=CC=CC=2)=C1 STIVJHUWVYOBNK-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/02—Compounds containing any of the groups, e.g. carbazates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
Opis wynalazkuDescription of the invention
Wynalazek dotyczy pewnych pochodnych 4-hydroksybifenylohydrazydu użytecznych jako związki pośrednie przy wytwarzaniu karboksylanu izopropylo-2-(4-metoksy-[1,1'-bifenylo]-3-ylo)hydrazyny (bifenazatu), sposobów ich wytwarzania oraz sposobów wytwarzania bifenazatu.The invention relates to certain 4-hydroxybiphenylhydrazide derivatives useful as intermediates in the preparation of isopropyl-2- (4-methoxy- [1,1'-biphenyl] -3-yl) hydrazine (biphenazate) carboxylate, methods for their preparation and methods for the preparation of biphenazate.
Tło wynalazkuBackground of the invention
W patencie Stanów Zjednoczonych Ameryki US-5367093 opisano sposób wytwarzania roztoczobójczej pochodnej fenylohydrazyny, karboksylanu izopropylo-2-(4-metoksy-[1,1'-bifenylo]-3-ylo)hydrazyny (bifenazatu), w sześcioetapowej procedurze która obejmuje niepożądane etapy wytwarzania i redukcji soli diazoniowej.U.S. Patent No. 5,367,093 describes a process for the preparation of the acaricidal phenylhydrazine derivative, isopropyl-2- (4-methoxy- [1,1'-biphenyl] -3-yl) hydrazine (biphenazate) carboxylate, in a six-step procedure that includes undesirable steps the production and reduction of the diazonium salt.
Pewne pochodne fenylohydrazyny można wytwarzać sposobami opisanymi w patencie Stanów Zjednoczonych Ameryki US-4864032 (aminowanie Grignard'a); w publikacji Mitchell, J. Org. Chem. 59, 682 (1994) (aminowanie bogatych w elektrony arenów); oraz w publikacji Lenarsic, J. Org. Chem. 64, 2558 (1999) (przez elektrofilowe azodikarboksylany).Certain phenylhydrazine derivatives can be prepared by the methods described in US Patent No. 4,864,032 (Grignard amination); in Mitchell, J. Org. Chem. 59, 682 (1994) (amination of electron-rich arenes); and in Lenarsic, J. Org. Chem. 64, 2558 (1999) (via electrophilic azodicarboxylates).
Celem niniejszego wynalazku jest dostarczenie nowych związków pośrednich użytecznych do wytwarzania bifenazatu. Celem niniejszego wynalazku jest także dostarczenie nowego sposobu wytwarzania bifenazatu.It is an object of the present invention to provide novel intermediates useful in the preparation of bifenazate. It is also an object of the present invention to provide a new process for the preparation of bifenazate.
Krótki opis wynalazkuBrief Description of the Invention
Niniejszy wynalazek dotyczy związków o wzorzeThe present invention relates to compounds of formula
w którym R oznacza wodór lub grupę estru izopropylowego; CO2CH(CH3)2) (IB).where R is hydrogen or an isopropyl ester group; CO2CH (CH3) 2) (IB).
Związki o wzorach IA i IB są użyteczne jako związki pośrednie przy wytwarzaniu bifenazatu.The compounds of formulas IA and IB are useful as intermediates in the preparation of bifenazate.
Niniejszy wynalazek dotyczy także sposobu wytwarzania związku o wzorze IA który to sposób obejmuje hydrolizowanie związku IB w obecności skutecznej ilości zasady w odpowiednim organicznym rozpuszczalniku.The present invention also relates to a process for the preparation of a compound of formula IA, the method comprising hydrolyzing compound IB in the presence of an effective amount of a base in a suitable organic solvent.
Niniejszy wynalazek dotyczy także sposobu wytwarzania bifenazatu który to sposób obejmuje metylowanie związku IA w obecności skutecznej ilości środka metylującego i zasady, w odpowiednim rozpuszczalniku.The present invention also relates to a method for the preparation of biphenazate, the method comprising methylating a compound IA in the presence of an effective amount of a methylating agent and a base in a suitable solvent.
Szczegółowy opis wynalazkuDetailed Description of the Invention
Związki według wynalazku można wytwarzać jak przedstawiono poniżej na schemacie 1.The compounds of the invention can be prepared as shown in Scheme 1 below.
PL 200 493 B1PL 200 493 B1
1. Aminowanie1. Amination
(IB)(IB)
4-hydroksybifenyl poddaje się reakcji z azodikarboksylanem di-izopropylu w obecności skutecznej ilości kwasu Lewisa w odpowiednim rozpuszczalniku dla wytworzenia związku IB. Użyteczne kwasy Lewisa obejmują, na przykład eterat trifluoroboru i chlorek glinu. Stężenie kwasu Lewisa w stosunku do 4-hydroksybifenylu w mieszaninie reakcyjnej może wynosić pomiędzy 1:0,2 do 1:1,1 (mol/mol), korzystnie wynosi 1:1,1 (mol/mol). Odpowiednie organiczne rozpuszczalniki te organiczne rozpuszczalniki które nie wpływają szkodliwie na reakcję aminowania i obejmują, na przykład octan etylu, dichlorometan, toluen i 1,2-dimetoksyetan. Temperatura mieszaniny reakcyjnej powinna wynosić od 0°C do 60°C, korzystnie w pobliżu temperatury pokojowej.4-hydroxybiphenyl is reacted with di-isopropyl azodicarboxylate in the presence of an effective amount of a Lewis acid in a suitable solvent to produce compound IB. The useful Lewis acids include, for example, boron trifluoride etherate and aluminum chloride. The concentration of Lewis acid with respect to 4-hydroxybiphenyl in the reaction mixture may be between 1: 0.2 to 1: 1.1 (mol / mol), preferably 1: 1.1 (mol / mol). Suitable organic solvents are those organic solvents which do not adversely affect the amination reaction and include, for example, ethyl acetate, dichloromethane, toluene and 1,2-dimethoxyethane. The temperature of the reaction mixture should be between 0 ° C and 60 ° C, preferably around room temperature.
2. Selektywna hydroliza2. Selective hydrolysis
Związek IB traktuje się skuteczną ilością zasady w odpowiednim organicznym rozpuszczalniku dla wytworzenia związku IA. Użyteczne związki zasadowe to te związki zasadowe które mogą hydrolizować ugrupowanie estrowe i obejmują, na przykład wodorotlenek sodu i wodorotlenek potasu. Stężenie zasady w stosunku do związku IB może wynosić pomiędzy 7:1 do 10:1 (mol/mol), korzystnie wynosi 9:1 (mol/mol). Odpowiednie organiczne rozpuszczalniki to te organiczne rozpuszczalniki które nie wpływają szkodliwie na reakcję hydrolizy i obejmują, na przykład toluen, sulfotlenek dimetylu i 1,2-dimetoksyetan. Korzystnie temperatura organicznego rozpuszczalnika powinna wynosić powyżej temperatury pokojowej a poniżej 110°C.Compound IB is treated with an effective amount of a base in a suitable organic solvent to produce compound IA. Useful basic compounds are those basic compounds which can hydrolyze the ester moiety, and include, for example, sodium hydroxide and potassium hydroxide. The base concentration with respect to compound IB may be between 7: 1 to 10: 1 (mol / mol), preferably it is 9: 1 (mol / mol). Suitable organic solvents are those organic solvents that do not adversely affect the hydrolysis reaction and include, for example, toluene, dimethyl sulfoxide, and 1,2-dimethoxyethane. Preferably, the temperature of the organic solvent should be above room temperature and below 110 ° C.
Związek IA następnie metyluje się w obecności skutecznej ilości środka metylującego i zasady, w odpowiednim organicznym rozpuszczalniku. Dla celów niniejszego wynalazku „ś rodek metylujacy” jest dowolnym związkiem który jest zdolny do pod stawienia grupy metylowej w miejsce atomu wodoru w grupie 4-hydroksylowej w związku IA. Użyteczne ś rodki metylujące obejmują, na przykład siarczan dimetylu i jodek metylu. Stężenie środka metylującego w stosunku związku IA może wynosić pomiędzy 1:1 do 1:1,2 (mol/mol), korzystnie wynosi 1:1 (mol/mol). Użyteczne związki zasadowe to te związki zasadowe które mogą odprotonować fenole i obejmują, na przykład węglan sodu i węglan potasu. Stężenie zasady w stosunku do związku IA może wynosić pomiędzy 1:1 do około. 3:1 (mol/mol), korzystnie wynosi około 2:1 (mol/mol). Odpowiednie organiczne rozpuszczalniki to te organiczne rozpuszczalniki które nie wpływają szkodliwie na reakcję metylowania i obejmują, na przykład toluen i aceton. Reakcja metylowania może być prowadzona w pobliżu temperatury pokojowej. Proces metylowania przykładowo przedstawiono poniżej na schemacie 2.Compound IA is then methylated with an effective amount of a methylating agent and a base in a suitable organic solvent. For the purposes of the present invention, a "methylating agent" is any compound that is capable of substituting a methyl group for a hydrogen atom on the 4-hydroxy group of IA. Useful methylating agents include, for example, dimethyl sulfate and methyl iodide. The concentration of the methylating agent in the ratio of compound IA may be between 1: 1 to 1: 1.2 (mol / mol), preferably it is 1: 1 (mol / mol). Useful basic compounds are those basic compounds that can deprotonate phenols and include, for example, sodium carbonate and potassium carbonate. The base concentration with respect to Compound IA may be between 1: 1 to about. 3: 1 (mol / mol), preferably about 2: 1 (mol / mol). Suitable organic solvents are those organic solvents which do not adversely affect the methylation reaction and include, for example, toluene and acetone. The methylation reaction can be conducted near room temperature. The methylation process is exemplified below in Scheme 2.
PL 200 493 B1PL 200 493 B1
Schemat 2Scheme 2
OH Η ΟOH Η Ο
OHOH
zasada/ rozpuszczalnik środek metylujący ( IA)base / solvent methylating agent (IA)
Bi fenazafBi phenazaph
Poniższe przykłady ilustrują rozwiązanie według wynalazku.The following examples illustrate the embodiment of the invention.
P r z y k ł a d 1P r z k ł a d 1
Wytwarzanie estru bis 1-metyloetylowego kwasu 1-(4-hydroksy-[1,1-bifenylo]-3-ylo)-hydrazynodikarboksylowego (związek IB)Preparation of 1- (4-hydroxy- [1,1-biphenyl] -3-yl) -hydrazine dicarboxylic acid bis 1-methyl ester (Compound IB)
Do roztworu 4-hydroksybifenylu (5,50 g) w octanie etylu (60 ml) w temperaturze pokojowej dodano eteratu trifluoroboru (4,1 ml). Otrzymaną mieszaninę ochłodzono do -5°C, dodano kroplami azodikarboksylan di-izopropylu (6,3 ml) i mieszano w tej temperaturze przez 30 minut a potem mieszano w temperaturze pokojowej przez dwie godziny. Potem mieszaninę zgaszono wodą (100 ml) i ekstrahowano octanem etylu (50 ml). Fazę organiczną oddzielono, wysuszono nad siarczanem magnezu i zatężano pod próż nią do pozostał o ś ci w postaci oleju który chromatografowano na ż elu krzemionkowym stosując 20-30% mieszankę octan etylu/heksan otrzymując związek IB jako beżowo zabarwione ciało stałe (10,65 g, 88% wydajności).To a solution of 4-hydroxybiphenyl (5.50 g) in ethyl acetate (60 ml) at room temperature was added boron trifluorate (4.1 ml). The resulting mixture was cooled to -5 ° C, di-isopropyl azodicarboxylate (6.3 ml) was added dropwise and stirred at this temperature for 30 minutes and then stirred at room temperature for two hours. The mixture was then quenched with water (100 ml) and extracted with ethyl acetate (50 ml). The organic phase was separated, dried over magnesium sulfate and concentrated in vacuo to an oil residue which was chromatographed on silica gel using 20-30% ethyl acetate / hexane to give compound IB as a beige colored solid (10.65 g , 88% efficiency).
1H-NMR (ppm, w CDCl3): m (12) 1,30; m (2) 5,04; m (2) 7,10; m (1) 7,32; dd (2) 7,43; m (3) 7,51-7,55; szer. s (1) 8,53. 1 H-NMR (ppm, in CDCl 3): m (12) 1.30; m (2) 5.04; m (2) 7.10; m (1) 7.32; dd (2) 7.43; m (3) 7.51-7.55; width sec (1) 8.53.
P r z y k ł a d 2P r z k ł a d 2
Wytwarzanie estru 1-metyloetylowego kwasu 2-(4-hydroksy-[1,1-bifenylo]-3-ylo)-hydrazynokarboksylowego (związek IA)Preparation of 2- (4-hydroxy- [1,1-biphenyl] -3-yl) -hydrazinecarboxylic acid 1-methylethyl ester (Compound IA)
Wodorotlenek potasu (5,0 g) dodano do mieszanej zawiesiny związku IB wytworzonego w przykładzie 1 (5,15 g) w toluenie (50 ml). Przez otrzymaną purpurową mieszaninę przepuszczano bąbelkami azot przez 20 minut, a potem ogrzewano w temperaturze 45°C przez 4 dni. Potem mieszaninę ochłodzono do temperatury 0°C i do mieszaniny dodawano 6M HCl aż pH mieszaniny wynosiło około 1. Potem mieszaninę ekstrahowano octanem etylu. Fazę organiczną oddzielono, przemyto solanką, wysuszono nad siarczanem magnezu i zatężano do brązowego ciała stałego. Po rekrystalizacji z toluenu otrzymano związek IA jako beżowo zabarwiony proszek (3,35 g, 85% wydajności).Potassium hydroxide (5.0 g) was added to a stirred suspension of compound IB prepared in Example 1 (5.15 g) in toluene (50 ml). The resulting purple mixture was bubbled with nitrogen for 20 minutes, then heated at 45 ° C for 4 days. The mixture was then cooled to 0 ° C and 6M HCl was added to the mixture until the pH of the mixture was about 1. The mixture was then extracted with ethyl acetate. The organic phase was separated, washed with brine, dried over magnesium sulfate, and concentrated to a brown solid. After recrystallization from toluene, IA was obtained as a beige-colored powder (3.35 g, 85% yield).
1H-NMR (ppm, w CDCl3): d (6) 1,81; septet (1) 5,04; szer. d (1) 5,91; szer. s (1) 6,61; d (1) 6,74; dd (1) 7,01; d(1) 7,14; dd (1) 7,32; dd (2) 7,42; dd (2) 7,61. 1 H-NMR (ppm, in CDCl 3): d (6) 1.81; septet (1) 5.04; br d (1) 5.91; bs (1) 6.61; d (1) 6.74; dd (1) 7.01; d (1) 7.14; dd (1) 7.32; dd (2) 7.42; dd (2) 7.61.
P r z y k ł a d 3P r z k ł a d 3
Wytwarzanie estru 1-metyloetylowego kwasu 2-(4-metoksy-[1,1-bisfenylo]-3-ylo)-hydrazynokarboksylowego (bifenazat)Preparation of 2- (4-methoxy- [1,1-bisphenyl] -3-yl) -hydrazinecarboxylic acid 1-methylethyl ester (biphenazate)
Przez zawiesinę związku IA przygotowanego w powyższym przykładzie 2 (2,63 g) i węglanu potasu (2,50 g) w acetonie (40 ml) przepuszczano bąbelkami azot przez 20 minut. Potem do zawiesiny dodano siarczan dimetylu (0,96 ml) w temperaturze pokojowej. Po 2 godzinach otrzymaną mieszaninę reakcyjną ochłodzono w łaźni z lodem. Do mieszaniny reakcyjnej w sposób ciągły dodawano 2 M HCl (około 30 ml) aż pH mieszaniny reakcyjnej osiągnęło wartość około 1. Potem mieszaninę reakcyjną zatężano dla usunięcia większości acetonu. Utworzone ciało stałe z zatężonej mieszaniny reakcyjnej odfiltrowano, przemyto wodą, heksanem i wysuszono na powietrzu z odsysaniem, wytwarzając bifenazat (2,60 g). Dane widma 1H-NMR były zgodne z danymi 1H-NMR podanymi dla bifenazatu w patencie Stanów Zjednoczonych Ameryki US-5367093.Nitrogen was bubbled through a suspension of Compound IA prepared in Example 2 above (2.63 g) and potassium carbonate (2.50 g) in acetone (40 ml) for 20 minutes. Thereafter, dimethyl sulfate (0.96 ml) was added to the suspension at room temperature. After 2 hours, the resulting reaction mixture was cooled in an ice bath. 2 M HCl (about 30 mL) was added continuously to the reaction mixture until the pH of the reaction mixture was about 1. The reaction mixture was then concentrated to remove most of the acetone. The solid formed from the concentrated reaction mixture was filtered, washed with water, hexane and air-dried under suction to give biphenazate (2.60 g). The 1 H-NMR data was consistent with the 1 H-NMR data reported for bifenazate in US Patent No. 5,367,093.
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| US09/413,072 US6093843A (en) | 1999-10-06 | 1999-10-06 | 4-hydroxybiphenyl hydrazide derivatives |
| PCT/US2000/026465 WO2001025191A1 (en) | 1999-10-06 | 2000-09-26 | 4-hydroxybiphenyl hydrazide derivatives |
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| JP (1) | JP3779616B2 (en) |
| KR (1) | KR100669572B1 (en) |
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| IL (2) | IL148629A0 (en) |
| PL (1) | PL200493B1 (en) |
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| US6706895B1 (en) | 2002-11-14 | 2004-03-16 | Uniroyal Chemical Company, Inc. | 4-methoxybiphenyl hydrazone derivatives |
| US7343196B2 (en) * | 2003-05-09 | 2008-03-11 | Ge Medical Systems Global Technology Company Llc | Cardiac CT system and method for planning and treatment of biventricular pacing using epicardial lead |
| US7592374B2 (en) * | 2005-03-03 | 2009-09-22 | Crompton Corporation | Insecticidal nitromethylene compounds |
| US7399757B1 (en) * | 2007-05-16 | 2008-07-15 | Chemtura Corporation | Pesticidal diazene oxide carboxylates |
| US7511029B2 (en) * | 2007-05-16 | 2009-03-31 | Chemtura Corporation | Pesticidal diazene oxide carboxylates |
| CN102344395A (en) * | 2011-07-28 | 2012-02-08 | 同济大学 | Synthesis method for bifenazate |
| CN102885074B (en) * | 2012-11-06 | 2013-12-11 | 江苏辉丰农化股份有限公司 | Acaricide composite with synergistic effect |
| CN103155939A (en) * | 2013-03-22 | 2013-06-19 | 青岛瀚生生物科技股份有限公司 | Clothianidin/Bifenazate compound insecticidal composition |
| US9758476B2 (en) | 2014-06-25 | 2017-09-12 | Council Of Scientific & Industrial Research | Ortho-alkynyl anilines and process for preparation thereof |
| CN105707118B (en) * | 2016-03-25 | 2018-02-06 | 江西正邦生物化工有限责任公司 | A kind of composition pesticide containing phosmet and Bifenazate |
| CN106831387B (en) | 2017-01-19 | 2020-12-29 | 上海科技大学 | A visible light-catalyzed direct oxidation of saturated carbon-hydrogen bonds |
| CN109988084B (en) * | 2019-04-23 | 2021-09-10 | 绍兴上虞新银邦生化有限公司 | Bifenazate synthesis method |
| CN110818596A (en) * | 2019-11-18 | 2020-02-21 | 合肥锦绣田园化工科技有限公司 | Semicarbazide compound and preparation and application thereof |
| CN115974727B (en) * | 2023-01-17 | 2024-03-12 | 青岛前线生物工程有限公司 | A kind of synthesis method of biphenylhydrazine |
| CN118344267A (en) * | 2024-04-17 | 2024-07-16 | 广东广康生化科技股份有限公司 | A new method for efficiently synthesizing bifenazate |
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| US4864032A (en) * | 1987-07-02 | 1989-09-05 | Ortho Pharmaceutical Corporation | Process for the preparation of indazoles |
| RO112860B1 (en) * | 1991-11-22 | 1998-01-30 | Uniroyal Chem Co Inc | Phenylhydrazine derivatives, pesticide and method for pest control |
| SK282306B6 (en) * | 1991-11-22 | 2002-01-07 | Uniroyal Chemical Company, Inc. | Phenylhydrazine derivatives, pesticidal preparation containing these compounds and method for controlling ineligible insects |
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| PT1218340E (en) | 2004-02-27 |
| DE60006703D1 (en) | 2003-12-24 |
| HUP0203538A3 (en) | 2005-10-28 |
| WO2001025191A1 (en) | 2001-04-12 |
| BR0014461A (en) | 2002-08-20 |
| AU7618000A (en) | 2001-05-10 |
| BR0014461B1 (en) | 2011-02-22 |
| AR079399A2 (en) | 2012-01-25 |
| AR025951A1 (en) | 2002-12-26 |
| JP2003511364A (en) | 2003-03-25 |
| ATE254598T1 (en) | 2003-12-15 |
| PL354483A1 (en) | 2004-01-26 |
| KR20020033822A (en) | 2002-05-07 |
| US6093843A (en) | 2000-07-25 |
| EP1218340A1 (en) | 2002-07-03 |
| DK1218340T3 (en) | 2004-03-29 |
| EP1218340B1 (en) | 2003-11-19 |
| CN1168708C (en) | 2004-09-29 |
| HU228227B1 (en) | 2013-02-28 |
| CA2385200C (en) | 2008-11-18 |
| CN1378529A (en) | 2002-11-06 |
| IL148629A0 (en) | 2002-09-12 |
| CA2385200A1 (en) | 2001-04-12 |
| ES2211613T3 (en) | 2004-07-16 |
| RU2242461C2 (en) | 2004-12-20 |
| HUP0203538A2 (en) | 2003-02-28 |
| AU783729B2 (en) | 2005-12-01 |
| CZ295841B6 (en) | 2005-11-16 |
| ZA200202185B (en) | 2003-08-27 |
| JP3779616B2 (en) | 2006-05-31 |
| KR100669572B1 (en) | 2007-01-15 |
| CZ20021185A3 (en) | 2003-11-12 |
| IL148629A (en) | 2006-10-31 |
| DE60006703T2 (en) | 2004-09-30 |
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